Tailoring liquid crystalline self-assembly and de Vries behavior of azulenes via lateral and core substitution

The azulene moiety is a highly attractive building block in optoelectronic applications due to its unique properties. For high-performing devices, the molecular orientation is crucial and can be controlled through liquid-crystalline self-assembly. Recent work showed that liquid crystalline derivatives bearing the 2-phenyl-azulene-1-nitrile core formed broad de Vries-type SmA and SmC phases. For exact understanding of the structure-property relationship, a series of 2-(hetero)aryl-azulenes has been synthesized varying the chain linkage, the lateral substituent, and the aromatic ring. Small changes of the molecular structure determined whether the orthogonal SmA phase or the tilted SmC phase is predominant. Implementation of alkyne chains instead of alkoxy chains resulted in the reduction of phase transition temperatures and formation of mesophases at room temperature. Furthermore, de Vries-like behavior was investigated and reduction values between R = 0.35 and 0.74 were measured which supported the hypothesis that in this system de Vries-like behavior is caused by steric repulsion of the lateral substituent. The control of the phase geometry by the molecular structure might be used for improved molecular orientation in optoelectronic materials.